N-acidoaminoalkyl-aminonaphthalene azo dyestuffs



Patented Oct. 12, 1926.

UNITEDSTATES PATENT OFFICE.

WALTER DUISBERG ,OE LEVERKUSEN,

NEAR COLOGNE, AND WINFRID 'HE'N'IRICH,

JOHANN HUISMAN N, AND LUDWIG ZEH, OF WIESDORF, NEAR COLOGNE, GERMANY,

ASSIGNORS TO GRASSELLI DYESTUFF COIREPOIRIATION, OF NEW YORK,

PORATION OF DELAWARE.

N. 'Y., A COR- N-ACIDOAMINOALKYL-AMINONAPHTHALENE AZO DYESTUFFSQ NoDrawing. Application filed June 8, 1925, Serial No. 35,769, and inGermany June 17, 1924.

\Ve have invented new and useful improvements in'N-acidoaminoalkyl-aminonaphthalene azo dyestuffs.

Our invention relates to the production I? of new dyestuffs particularlyadapted for the dyeing of animal fibres. v o have found that azocompounds of the type i v D-N:N-C, H NHANHR in which formula DN-:N- isthe diazo compound and in which the coupling'coinpound is anN-aminoalkyl-Q-aminonaphthal'ene with the external amino group furthersubstituted, dye animal fibres in an acid,.:bath various shades whichare distinguished by excellent fastness, specially to light and milling:the dyeings are furthermore exceedingly level. The shades range from red{to violet to blue to a large variety of brown iues.

The N -aminosubstituted alkyl 2 amini'iaphthalenes can be represented bythe general formula In this type of compounds as embodied in ourinvention the naphthalene nucleus can be further substituted byhydroxyl, sulfo groups, etc. Amongst the alkyl groups, designed by A inthe above formula, which we have found easily accessible and valuableare the ethyl, propyl, butyl, etc. groups. The substituent R in theexternal amino group represents either an acidyl group such as urylCONI-I .jacetyl COCH benzoyl CO-C H sulfotoluol SO (LIL-CH chloracetylCOCH Cl or an acid radical such as CH COOH, wh ch latter may beintroduced into this amino group by reacting upon same with an acidic.compound having a labile chlorine atom linked directly to the carbonchain, as for instance chloraeetie acid CICH COOH, in presence of aneutralizing agent.

For the purpose of this inventionwe will call acido these two types of'substituent as indicated in the above formula'by the letter R. h

While our new dyestuffs are particularly ,valuable for the dyeing ofanimal fibres, we have found that if theN-acidoaminoalkylaminonaphthalenc contains no sulfo or carboxylic group,and if the diazo compound contains only one sulfothe azo dyestuffsobtained will dye cellulose ester material, particularly celluloseacetate silks, very bright and fast shades.

The type of diazo compound-used to produce our new dyestuffs is oflittle importance, though offcourse variations in the chemicalconstitution of same will, to a certain extent, influence the shade andeventually modifv the fastness properties, which are otherwise mainlydue to the particular substitution in the coupling compound. The mostvaluable shades have so, far been obtained with diazo compounds of thebenzene series, though diazo-naphthalenes may likewise be used. 1

or carboxyl group The process of producing these new azo dyestuffsconsists 1n coupling either in acid,

neutral or alkaline solution diazo compounds withN-aminoalkyl-2-aminonaphthalenes, and treating the so-obtained primarydyestuffs with a reagent capable of substituting the external aminogroup by an acido radical. As such reagents acetic anhydride,chloracetylchloride, p-toluolsulfochloride, chlor-acetic acid have beenfound most convenient. The dyestufl is then salted out of solution,filtered off and dried.

While this is i". most cases our referred process it might in certaincases e advisvery rapidly.

alkyl-2-amino-aminonaphthalene or a deacid et-ethylaminoaniline andN-aminoethylrivative of same is obtained. V 2- amino- 1; amino-8-naphthol-3 6-disulfonic In order to further illustrate our invenacidis obtained.

tion, the following examples are given, the Ewample .4.-168 parts5-nitro-2-anisidine parts being by weight. are diazotized in the usualWay and the E ma mplc 1.301 parts Q- L-dinitroanilinediazo solution soobtained is run into an ice 6-sulfonate of potassium are diazotized andcold solution of 384 parts N-aminoethyl-Q- the diazo obtained coupled inmineral acid amino-8-naphthol-3-6-disulfonate of sodium, containing anexcess of sodium bicarbonate. After the coupling is finished thesolution is heated-to (SO-70 C. and acetyl- The free dyestuff acidobated with 100-120 parts acetic anhydride. tained is filtered'ofi anddissolved in hot The dyestuff is salted out hot, filtered off water witha little alkali. To this solution and dried. It is a black powder,easily 100-120 parts acetic anhydride are added at soluble in water anddyes wool level olive- 65-75 C. and the reaction mass allowed to brownshades of excellent fastness to light cool. The new dyestufi dyescellulose aceand milling. It can be represented by the tate silk clearblue shades and wool greenish formula blue shades. It is in form of itssodium solution with 186 parts N-aminoethyl-2- aminonaphthalenedissolved in dilute hydrochloric acid. The coupling proceeds 00H, 2 salta dark powder, easily soluble in water and has most llkely the formula Ono, NH-oHmHr-Nn-oo-cm om N=N-/ H0 g N NHCHZCH,"NH-CO-CHV O;Na

By reduction with zinc and hydrochloric mo 503m acid a t-riaminobenzenesulfonic acid and the diazo compound obtained 'c'oupled N in th l-g g itL hth l i 1 By reduction with zinc and hydrochloric obtained. I I aciddlamino a-nisol and N-aminoethyl-2- Ewample .Z.-301 parts2-4-dinitroaniline 1 9 P sulfoll c 6v-sulfonate of potassium arediazotized and acld are ey i In the table below a number of other comi lid l ti ith 228 Parts N- binations illustrating our invention aredeacetylaminoethyl-Q-aminonaphthalene. lhe scllbedcoupling proceedsrapidly. The reaction mass is made slightly alkaline; salted out andCoupling substib Coupling Shades Shages the dyestufi' ls olated 1n theusual way. It cotmpoun compound. uent R. periormad on 0911211058 1sidentical w1th the product obtained in mm acetate- Example 1. x

i 4-nitroan1- N-amino- AcetyL- Mineral Violet... Rcddlsh- Example 3. 178parts 4 acetylethylami wimp my; 8cm Violet.

noanillne are diazotlzed H1 the usual way fonicacid. in and coupled inslightly mineral acid solution mi i w p f PQ Y 'Q 4-nitroani- N-amiilo-Aoatyl Mineral Violet.-. naphthol-3-6-d1sulfon1o acid; the intermepug-mpg g gan diate dyestuff 1s then 'acetylat-ed and Isolated omega n1 .11-1n the usual way. It is in form of its-sog q gg-g chum salt a darkpowder, easily soluble in acidwater w1th a reddish brown color. It dyest-nitroani- N-amino- Benzoyl. Mineral Violet--- wool very level,reddish-brown full shades 25552331 Ka i? of exce1lentfastness t0 llghtand milling. f g g l It has most probably. the formula 7 sulgmic /C1Hl vN N 4-nitroam- N-amino- Chlor- Mineral Vio1et \C0 CH 1me-2-su1- ethYI-Z-acetyl. acid. fonicacid. naph th yl7- r amine-- 3 sulfonic NH-GH -CH-NII-GOGH. acid knitroanb N-amino-- P-tolu- Mineral Violet...

line-z-sulethyl-Z- 01311110. acid. fonicacid. naphamme- N80: OINB um 1acid. 7

By reduction with zinc and hydrochloric M-nitropound with Shades oncellulose acetate.

Shades wool.

Diazo compound from- Substituent R.

4-nitroaniline-zsulethyl-2- ionicacid.

Acetic." Mineral Violet".

' acid.

i sulionic- 2-nitro-4- ,aminotoluol.

Reddish Acetyl brown.

Mineral acid.

8-naph- Acetyl brown.

Mineral acid.

Mineral brown.

aniline. ethyl-2- acid,

Neutral brown.

M-nitroaniline.

amino- Reddish brown.

Alkaline- S-naphthol-3- G-dislll- N-aminoethyl-2- amino- S-na h the -3-fl-disulionic acid.

4-nitro-2- Acetyl. Alkaline;

-R di 11 l anisidine. ed S brown.

We claim 1 In processes of producing N-acidoammoalkyl-2-aminonaphthaleneazo dyestuffs the'steps' comprising coupling a diazo comanN-aminoalkylQ-aminonaphthalene compound and substitutin the externalamino group by an'acido ra stantially as described.

2. In processes of reducing N-acidoaminoalkyl-2aminonaph5ia1ene azodyestuffs the steps comprising coupling a dia-z'o compound of thebenzene series with an N-aminoalkyl- Q-aminonaphthalene compound andsubstituting the external amino group by an acido radical, substantiallyas described;

3. In processes of producing N -acidoaminoalkyl-2-aminonaphthalene azodyestuffs the steps comprising coupling in 1aminoethyl-2-aminonaphthalene ical, 'submin- Y eralacid solution a diazopompound of the benzene series with an N -aminoalkyl 2- aminonaphthalenecompound and substitutmg the external amino group by an acidoradicaL-substantially as described.

'4. In processes of producing N-acidoazo dyestufls'the steps comprisingcoupling a diazo compound of the benzene series with an N-aminoethyl-2-aminonaphthalene compound and substituting the externalamino group by an acido radical, substantially as described.

5. In processes of producing N -acetylaminoethyl-2-aminonaphthalene azodyestufi's the steps comprising coupling in mineral acid solution adiazo compound of the benzene series with anN-aminoethyl-Q-aminonaphthalene compound and acetyla ting the externalamino group.

6. In processes of producing4-acetylethyl-' amino-benzene-Lazo-(N-ace'tylaminoethyl)-- 2-amino-8-naphthol-3-6-disulfonic acid the stepscomprising coupling .t-acetylethylamino-l-diazobenzene in mineral acidsolution with N-aminoethyl-2-amino-8-naphthol-3-6- disulfonic acid andtreating the resulting product with acetic anhydride to effectacetylation of the external amino group.

7. As new products N-acidoaminoalkyl-2- aminomaphthalene azo dyeshtuffsof the general formula D N=N-C H NHA-NHR in which formula DN:N' standsfor a diazo compound, A for an alkylradical and R *for an acido radical,which dyestuffs are generally dark powders, soluble in water,

dyeing wool from red to violet to blue to brown fast and level shadesand yielding by reduction,,as for instance with zinc and hydrochloricacid, an amine and an N-aminoalkyd-2-aminonaphthylamine compound or aderivative of same.

8. As new productsN-acidoaminoethyl-2- ami'nonaphthalene azo dyestufl'sof the general formula in which formula D-N=N stands for a diazocompound and R for an acido radical, which dyestufl s are generally darkpowders, soluble in water, dyeing wool from red to violet to blue tobrown exceedingly fast and level shades and which by reduction, as forinstance by zinc and hydrochloric acid, yield an amine and anN-aminoethyl-Q-aminonaphthylamine compound or a derivative of same.

7 9. As new products N-acetylaminoethyl-2- amin'onaphthylene azodyestuffs of the general formula I DN=N-C H NH-CH a 2 H Hs ingly fast inwhich formula D-N::N stands for a diazo' compound, which dyestuffs aregenerally dark powders, soluble in water, dyeing wool from red to violetto blue to brown exceedingly fast and level shades and which byreduction as for instance with zinc and hydrochloric acid yield an amineand an N- aminoethyl 2 aminonaphthylamine com pound.

.10. As new products N-acetylaminoethyl- Q-aminonaphthalene azodyestuffs of the general formula in which lD-N:N stands for a diazocompound, which dyestufis are generally dark powders soluble in water,dyeing wool from red to violet to blue to brown exceedand level shades"and which by reduction as for instance with zinc and hydrochloric acidyield an amine and an N-aminoethyl-2-amino-l-naphthylamine compound.

11. As new products N-acetylaminoethyl- 2- aminonaphthalene azodyestuffs of the general formula N-D in which lD-N=N stands for amononuseries and set our hands.

3038/ soul which in form of' its sodium salt is a black powder, solublein water, dyeing wool reddish brown level shades, milling and which byreduction as for instance with zinc and hydrochloric acid yieldsl-ethylaminoaniline and N-amino ethyl- 2-amino-l-naphthylamine 3 6disulitonic acid.

lin testimony whereof we have hereunto WALTER DUISBERG. WENFRIDHENTRIOH. JOHANN HUISMANN. LUDWIG ZEH.

fast to light and till

